JP4868981B2 - Antistatic agent for thermoplastic polymer, antistatic method for thermoplastic polymer molding, and antistatic thermoplastic polymer molding - Google Patents

Description

  The present invention relates to an antistatic agent for thermoplastic polymers, an antistatic method for thermoplastic polymer moldings, and an antistatic thermoplastic polymer molding. Various thermoplastic polymers are widely used as thermoplastic polymer moldings such as films, sheets, containers, and casings. However, it is known that such a thermoplastic polymer molded body may cause various electrostatic disturbances during its production and processing steps and during its use. In the production or processing of a thermoplastic polymer molded body, it is required to use an antistatic agent that can sufficiently prevent such electrostatic damage. On the other hand, in recent years, from the viewpoint of avoiding environmental pollution and at the same time reducing manufacturing and processing costs, recycle wastes and used thermoplastic polymer moldings produced in the manufacturing and processing steps of thermoplastic polymer moldings. However, for this purpose, it is required that the antistatic agent used in the production or processing of the thermoplastic polymer molded body as described above does not cause a problem in such reuse. . The present invention relates to an antistatic agent for thermoplastic polymers that meets the above requirements, an antistatic method for a thermoplastic polymer molding using the same, and an antistatic thermoplastic polymer molding using the same.

  Conventionally, a wide variety of ionic polymer compounds are generally used as antistatic agents for thermoplastic polymers. However, ionic polymer compounds that have been conventionally used as an antistatic agent for thermoplastic polymers are generally poor in heat resistance. As a result, the thermoplastic polymer molded article has a sufficiently durable charge. 2) When it is used in the production or processing of thermoplastic polymer moldings, it is colored when it is remelted to produce scraps or used thermoplastic polymer moldings. 3) There is a problem that the applicability to the thermoplastic polymer molding is inferior.

As an antistatic agent for thermoplastic polymers that improves the above problems, polycation polymers having a plurality of nitrogen atoms in the molecule have been proposed (see, for example, Patent Documents 1 to 5). However, although the polycation polymer conventionally proposed as an antistatic agent for thermoplastic polymers has a correspondingly improved heat resistance, it can impart an appropriate antistatic property to a thermoplastic polymer molded article. Insufficient antistatic properties under low humidity conditions, 2) Inferior coatability as above, 3) Easy transfer from the coated surface of the thermoplastic polymer molding using the same, 4) Use When the molded thermoplastic polymer is a film or sheet, they are likely to block each other, and when the molded thermoplastic polymer is a container or casing, the There is a problem in some way, such as a feeling of stickiness.
JP-A-1-146931 JP-A-1-174538 JP-A-8-281891 JP-A-9-31224 JP 2003-136661 A

  The problem to be solved by the present invention is that the thermoplastic polymer molded article can be provided with sufficiently durable antistatic properties even under low humidity conditions, and at the same time, the reusability of the thermoplastic polymer molded article, etc. Desirable excellent properties such as applicability to plastic polymer moldings, non-transferability from thermoplastic polymer moldings, blocking resistance between thermoplastic polymer moldings, and non-tackiness of thermoplastic polymer moldings The object of the present invention is to provide an antistatic agent for thermoplastic polymers that exhibits performance, an antistatic method for a thermoplastic polymer molding using the same, and an antistatic thermoplastic polymer molding using the same.

  Therefore, as a result of researches to solve the above problems, the present inventor, as an antistatic agent for thermoplastic polymers, is a structural unit formed from a specific monomer having a quaternary ammonium base in the molecule. And a vinyl copolymer having a predetermined number average molecular weight, having a predetermined ratio of a structural unit formed from a specific monomer having a polyoxyalkylene group and a structural unit formed from a specific crosslinkable monomer It has been found that it is suitable to use.

  That is, the present invention relates to an antistatic agent for thermoplastic polymers, comprising one or more selected from the following vinyl copolymer M and the following vinyl copolymer N.

  Vinyl copolymer M: 70 to 95 mol% of a structural unit A formed from the monomer represented by the following chemical formula 1 in the molecule, and a structural unit B formed from the following polyoxyalkylene-modified monomer A vinyl copolymer having a number average molecular weight of 7000 to 100,000, having 1 to 10 mol% and 4 to 20 mol% (100 mol% in total) of structural units C formed from the following crosslinkable monomers

  Vinyl copolymer N: 70 to 94 mol% of a structural unit A formed from the monomer represented by the following chemical formula 1 in the molecule, and a structural unit B formed from the following polyoxyalkylene-modified monomer 1 to 10 mol%, 4 to 20 mol% of a structural unit C formed from the following crosslinkable monomer and the monomer represented by the following chemical formula 1 or the following polyoxyalkylene-modified monomer or the following A vinyl copolymer having a number average molecular weight of 7000 to 100,000 having 1 to 25 mol% (total of 100 mol%) of a structural unit D formed from a monomer copolymerizable with a crosslinkable monomer

  Polyoxyalkylene-modified monomer: one or more selected from polyoxyalkylene-modified monomers represented by the following chemical formula 2

  Crosslinkable monomer: crosslinkable monomer represented by the following chemical formula 5, crosslinkable monomer represented by the following chemical formula 6, crosslinkable monomer represented by the following chemical formula 7, and chemical formula 8 below One or more selected from the crosslinkable monomers shown

In Chemical Formula 1 to Chemical Formula 8,
R ¹ , R ⁵ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ : hydrogen atom or methyl group R ² , R ³ , R ⁴ : hydroxyalkyl having 2 or 3 carbon atoms in hydrogen atom, methyl group or alkyl group Group (however, at least two of R ^{2 to} R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in an alkyl group)
R ⁶ : an alkyl group having 1 to 12 carbon atoms R ¹² : a hydrogen atom or an alkyl group having 1 to 6 carbon atoms R ¹³ : a hydrogen atom, a methyl group or a carboxyl group A: a carbonyloxy group or a carbonylamino group B: 2 carbon atoms 6 alkylene group D ^1: residue obtained by removing all hydroxyl groups from polyethylene glycol having a polyoxyethylene group which is a total of 9-35 oxyethylene units in the molecule X ^-: nitrate ion group or an alkyl group 1 to 4 alkylsulfonic acid ion groups having 1 to 4 carbon atoms Y ¹ : a hydrogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, an organic group having 3 to 10 carbon atoms having an epoxy group, or a total of 1 to 3 (Poly) oxyalkylene diol having a (poly) oxyalkylene group composed of oxyethylene units and / or oxypropylene units Residue excluding one hydroxyl group Y ² : An epoxy group-containing organic group having 3 to 10 carbon atoms or a total of 1 to 3 oxyethylene units and / or oxypropylene units in the molecule (poly) Residue obtained by removing one hydroxyl group from a (poly) oxyalkylenediol having an oxyalkylene group Y ³ : a hydrogen atom, an organic group having 3 to 10 carbon atoms having an epoxy group, or a total of 1 to 3 oxyethylene groups in the molecule Residue obtained by removing one hydroxyl group from a (poly) oxyalkylenediol having a (poly) oxyalkylene group composed of units and / or oxypropylene units

The present invention is also characterized in that the antistatic agent for thermoplastic polymers according to the present invention described above is adhered in a ratio of 0.01 to 3 g per 1 m ² of the surface of the thermoplastic polymer molded body. The present invention relates to an antistatic method for a plastic polymer molded body.

Further, the present invention is characterized in that the above-mentioned antistatic agent for thermoplastic polymer according to the present invention is adhered in a ratio of 0.01 to 3 g per 1 m ² of the surface of the thermoplastic polymer molding. The present invention relates to a preventive thermoplastic polymer molding.

  First, the antistatic agent for thermoplastic polymers according to the present invention (hereinafter simply referred to as the antistatic agent of the present invention) will be described. The vinyl copolymer used as the antistatic agent of the present invention includes a structural unit A formed from the monomer represented by Chemical Formula 1, a structural unit B formed from the polyoxyalkylene-modified monomer, and a crosslinkable monomer. A vinyl copolymer M comprising a structural unit C formed from a polymer, a structural unit A formed from a monomer represented by Chemical Formula 1, a structural unit B formed from a polyoxyalkylene-modified monomer, and a crosslinking property Monomer (hereinafter simply referred to as other monomer) copolymerizable with the structural unit C formed from the monomer and the monomer represented by Chemical Formula 1 or a polyoxyalkylene-modified monomer or a crosslinkable monomer. 1 or 2 or more selected from the vinyl copolymer N composed of the structural unit D formed from the above), the above vinyl copolymer M and the vinyl copolymer N.

  In the vinyl copolymer M, the structural unit A is formed from a monomer represented by Chemical Formula 1. In the monomer represented by Chemical Formula 1, examples of A in Chemical Formula 1 include a carbonyloxy group and a carbonylamino group. Examples of B in Chemical Formula 1 include alkylene groups having 2 to 6 carbon atoms such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group, and ethylene group or trimethylene group is preferable.

In the monomer represented by Chemical Formula 1, R ^{1 in} Chemical Formula ¹ is a hydrogen atom or a methyl group, and R ² , R ³ , and R ⁴ in Chemical Formula 1 are carbon atoms of a hydrogen atom, a methyl group, or an alkyl group. It is a hydroxyalkyl group having 2 or 3 numbers, and at least two of R ^{2 to} R ⁴ are methyl groups or alkyl groups having 2 or 3 carbon atoms in the alkyl group. That is, when R ² is a hydrogen atom, R ³ and R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in the alkyl group. Similarly, when R ³ is a hydrogen atom, R ² and R ⁴ Is a hydroxyalkyl group having 2 or 3 carbon atoms in the methyl group or alkyl group. Similarly, when R ⁴ is a hydrogen atom, R ² and R ³ are those in which the methyl group or alkyl group has 2 or 3 carbon atoms. A hydroxyalkyl group;

In the monomer represented by the addition of 1, in Formula 1 X ^- as is 1) nitrate group, 2) methyl sulfonate ion group, ethyl sulfonate ion group, propyl sulfonic acid ion group, isopropyl sulfonate ion Group, alkyl sulfonate ion group having 1 to 4 carbon atoms such as butyl sulfonate ion group, isobutyl sulfonate ion group and the like, preferably nitrate ion group or methyl sulfonate ion group, and methyl sulfonate ion group More preferred.

  Specific examples of the monomer represented by Chemical Formula 1 described above include 1) acryloyloxyethyltrimethylammonium methylsulfonate, acryloyloxypropyldimethylammonium ethylsulfonate, acryloyloxypropyl 2-hydroxyethyldimethylammonium nitrate, Monomer when A in chemistry 1 is a carbonyloxy group, such as acryloyloxypropyltrimethylammonium nitrate, methacryloyloxybutyltrimethylammonium methylsulfonate, methacryloyloxyhexyldi (2-hydroxyethyl) ammonium nitrate, 2) Acryloylaminoethyltrimethylammonium methylsulfonate, acryloylaminopropyldimethylammonium ethylsulfonate, acryloylaminopropyl A in Chemical Formula 1 such as pill 2-hydroxyethyldimethylammonium nitrate, acryloylaminopropyltrimethylammonium nitrate, methacryloylaminobutyltrimethylammonium methylsulfonate, methacryloylaminohexyldi (2-hydroxyethyl) ammonium nitrate is a carbonylamino group Monomers in some cases are mentioned.

  In the vinyl copolymer M, the structural unit B is formed from a polyoxyalkylene-modified monomer. Such a polyoxyalkylene-modified monomer is one or more selected from polyoxyalkylene-modified monomers represented by Chemical Formula 2.

In the polyoxyalkylene-modified monomer represented by Chemical Formula 2, R ^{5 in} Chemical Formula 2 is a hydrogen atom or a methyl group. R ^{6 in} Chemical Formula 2 is a carbon such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or a dodecyl group. Although it is a C1-C12 alkyl group, a methyl group is preferable especially. Further, D ^{1 in} Chemical Formula 2 is a residue obtained by removing all hydroxyl groups from polyoxyethylene diol having a polyoxyethylene group composed of a total of 9 to 35 oxyethylene units in the molecule.

  Specific examples of the polyoxyalkylene-modified monomer represented by Chemical Formula 2 described above include methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, propoxypolyethyleneglycol (meth) acrylate, butoxypolyethyleneglycol (meta ) Acrylate, pentoxypolyethylene glycol (meth) acrylate, hexyloxypolyethylene glycol (meth) acrylate, etc., among which methoxypolyethylene glycol (meth) acrylate is preferred.

  In the vinyl copolymer M, the structural unit C is formed from a crosslinkable monomer. Such a crosslinkable monomer includes a crosslinkable monomer represented by Chemical Formula 5, a crosslinkable monomer represented by Chemical Formula 6, a crosslinkable monomer represented by Chemical Formula 7, and a crosslinkable monomer represented by Chemical Formula 8. Although it is one or two or more selected from the body, as the crosslinkable monomer, those represented by Chemical formula 5 are preferred.

In the crosslinkable monomer represented by Chemical formula 5, R ^{11 in} Chemical formula 5 is a hydrogen atom or a methyl group. In addition, R ^{12 in} Chemical Formula 5 is 1) a hydrogen atom, 2) an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, or a hexyl group. Among them, a hydrogen atom, a methyl group or a butyl group is preferable.

  Specific examples of the cross-linkable monomer represented by Chemical Formula 5 described above include N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, N- Tertiary butyloxymethyl acrylamide, N-hexyloxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N-tertiary butyloxymethyl methacrylamide, N-hexyloxymethyl Although methacrylamide etc. are mentioned, N-methylol acrylamide, N-methoxymethyl acrylamide, N-butoxymethyl acrylamide etc. are especially preferable.

In the crosslinkable monomer represented by Chemical formula 6, R ^{13 in} Chemical formula 6 is a hydrogen atom, a methyl group or a carboxyl group. R ^{14 in} Chemical Formula 6 is a hydrogen atom or a methyl group. Further, Y ^{1 in} Chemical Formula 6 includes 1) a hydrogen atom, 2) a hydroxyalkyl having 1 to 6 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group. Group, 3) C 3 -C 3 having an epoxy group such as glycidyl group, 2,3-epoxybutyl group, 2,3-epoxy-2-methylpropyl group, 2- (3,4-epoxycyclohexyl) ethyl group 10 organic groups, 4) a residue obtained by removing one hydroxyl group from (poly) oxyethylene diol having a (poly) oxyethylene group composed of 1 to 3 oxyethylene units in the molecule, 1 in the molecule One hydroxyl group is removed from a (poly) oxypropylene diol having a (poly) oxypropylene group composed of 3 oxypropylene units. Residues, one from a (poly) oxyethylene (poly) oxypropylene diol having a (poly) oxyethylene (poly) oxypropylene group composed of a total of 2 or 3 oxyethylene units and oxypropylene units in the molecule. Examples include residues obtained by removing one hydroxyl group from (poly) oxyalkylenediol, such as residues obtained by removing one hydroxyl group, among which 1) hydrogen atom, 2) hydroxyethyl group, 3) glycidyl group, 2 , 3-epoxybutyl group, 2,3-epoxy-2-methylpropyl group and other organic groups having 3 or 4 carbon atoms are preferable, and glycidyl group is more preferable.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 6 described above include acrylic acid, methacrylic acid, crotonic acid, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, hydroxymethyl crotonate 2-hydroxyethyl crotonate, 3-hydroxypropyl crotonate, 4-hydroxybutyl crotonate, 5-hydroxy Ntilcrotonate, 6-hydroxyhexylcrotonate, glycidyl acrylate, glycidyl methacrylate, 2,3-epoxybutyl acrylate, 2,3-epoxybutyl methacrylate, 2,3-epoxy-2-methylpropyl acrylate, 2,3- Epoxy-2-methylpropyl methacrylate, glycidyl crotonate, polyoxyethylene acrylate, polyoxypropylene acrylate, oxyethylene oxypropylene acrylate, polyoxyethylene oxypropylene acrylate, oxyethylene polyoxypropylene acrylate, poly methacrylate Oxyethylene, polyoxypropylene methacrylate, oxyethylene oxypropylene methacrylate, polyoxyethylene oxypropylene methacrylate, meta Examples include oxyethylene polyoxypropylene oxylate, polyoxyethylene crotonate, polyoxypropylene crotonate, oxyethylene oxypropylene crotonate, polyoxyethylene oxypropylene crotonate, oxyethylene polyoxypropylene crotonate, among others Acrylic acid, 2-hydroxyethyl methacrylate, and glycidyl methacrylate are preferred.

In the crosslinkable monomer represented by Chemical formula 7, R ^{15 in} Chemical formula 7 is a hydrogen atom or a methyl group. As Y ^{2 in} Chemical Formula 7, 1) epoxy such as glycidyl group, 2,3-epoxybutyl group, 2,3-epoxy-2-methylpropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, etc. An organic group having 3 to 10 carbon atoms having a group, 2) one hydroxyl group was removed from a (poly) oxyethylene diol having a (poly) oxyethylene group composed of 1 to 3 oxyethylene units in the molecule Residue, residue obtained by removing one hydroxyl group from (poly) oxypropylene diol having (poly) oxypropylene group composed of 1 to 3 oxypropylene units in the molecule, 2 or 3 in total (Poly) oxyethylene (poly) oxypropylene having (poly) oxyethylene (poly) oxypropylene groups composed of oxyethylene units and oxypropylene units Examples include residues obtained by removing one hydroxyl group from (poly) oxyalkylenediol, such as residues obtained by removing one hydroxyl group from pyrenediol, among which glycidyl group, 2,3-epoxybutyl group, 2, A C3-C4 organic group having an epoxy group such as a 3-epoxy-2-methylpropyl group is preferred, and a glycidyl group is more preferred.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 7 described above include vinyl glycidyl ether, vinyl = 2,3-epoxybutyl ether, vinyl = 2,3-epoxy-2-methylpropyl ether, methallyl glycidyl ether. , Isopropenyl = 2,3-epoxybutyl ether, isopropenyl = 2,3-epoxy-2-methylpropyl ether, α-vinyl-ω-hydroxy (polyoxyethylene), α-vinyl-ω-hydroxy (polyoxypropylene) ), Α-vinyl-ω-hydroxy (oxyethyleneoxypropylene), α-vinyl-ω-hydroxy (polyoxyethyleneoxypropylene), α-vinyl-ω-hydroxy (oxyethylene polyoxypropylene), α-isopropenyl -Ω-hydroxy (polyoxyethylene), α-i Propenyl-ω-hydroxy (polyoxypropylene), α-isopropenyl-ω-hydroxy (oxyethyleneoxypropylene), α-isopropenyl-ω-hydroxy (polyoxyethyleneoxypropylene), α-isopropenyl-ω-hydroxy (Oxyethylene polyoxypropylene) and the like are mentioned, among which vinyl glycidyl ether is preferable.

In the crosslinkable monomer represented by Chemical formula 8, R ^{16 in} Chemical formula 8 is a hydrogen atom or a methyl group. Y ^{3 in} Chemical Formula 8 includes 1) hydrogen atom, 2) glycidyl group, 2,3-epoxybutyl group, 2,3-epoxy-2-methylpropyl group, 2- (3,4-epoxycyclohexyl). An organic group having 3 to 10 carbon atoms having an epoxy group, such as an ethyl group, 3) from a (poly) oxyethylene diol having a (poly) oxyethylene group composed of 1 to 3 oxyethylene units in the molecule Residue excluding one hydroxyl group, residue excluding one hydroxyl group from (poly) oxypropylenediol having (poly) oxypropylene group composed of 1 to 3 oxypropylene units in the molecule, in the molecule (Poly) oxyethylene having a (poly) oxyethylene (poly) oxypropylene group composed of a total of 2 or 3 oxyethylene units and oxypropylene units ( Examples include residues obtained by removing one hydroxyl group from polyoxyalkylene diol, such as residues obtained by removing one hydroxyl group from poly) oxypropylene diol, among which glycidyl group, 2,3-epoxybutyl group, 2 , A 3- or 4-carbon organic group having an epoxy group such as 3-epoxy-2-methylpropyl group is preferred, and a glycidyl group is more preferred.

  Specific examples of the crosslinkable monomer represented by Chemical Formula 8 described above include allyl alcohol, allyl glycidyl ether, allyl = 2,3-epoxybutyl ether, allyl = 2,3-epoxybutyl ether, allyl = 2,3- Epoxy-2-methylpropyl ether, methallyl glycidyl ether, methallyl = 2,3-epoxybutyl ether, methallyl = 2,3-epoxy-2-methylpropyl ether, α-allyl-ω-hydroxy (polyoxyethylene), α -Allyl-ω-hydroxy (polyoxypropylene), α-allyl-ω-hydroxy (oxyethyleneoxypropylene), α-allyl-ω-hydroxy (polyoxyethyleneoxypropylene), α-allyl-ω-hydroxy (oxy) Ethylene polyoxypropylene), α-methallyl-ω- Droxy (polyoxyethylene), α-methallyl-ω-hydroxy (polyoxypropylene), α-methallyl-ω-hydroxy (oxyethyleneoxypropylene), α-methallyl-ω-hydroxy (polyoxyethyleneoxypropylene), etc. Among them, allyl alcohol and allyl glycidyl ether are preferable.

  The vinyl copolymer M used as an antistatic agent of the present invention is obtained by radical copolymerization of the monomer represented by Chemical Formula 1 described above, a polyoxyalkylene-modified monomer, and a crosslinkable monomer. It is done. The radical copolymerization itself can be carried out by a known method, usually in an aqueous solution using water or a mixed solvent of water and a water-soluble organic solvent. For example, the monomer represented by Chemical Formula 1, the polyoxyalkylene-modified monomer, and the crosslinkable monomer were dissolved in water, and an aqueous solution containing 10 to 45% by mass of these monomers as a total amount was prepared. Thereafter, in a nitrogen gas atmosphere, a radical initiator is added thereto, and a radical copolymerization reaction is performed at 50 to 80 ° C. for 4 to 8 hours. The radical initiator to be used is not particularly limited as long as it decomposes at a polymerization reaction temperature and generates radicals, but a water-soluble radical initiator is preferably used. Examples of the water-soluble radical initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide, 2,2-azobis (2-amidinopropane) dihydrochloride, and the like. These can also be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid, or an amine.

  The vinyl copolymer M is obtained by the radical copolymerization described above, but the polyoxyalkylene-modified monomer contains 70 to 95 mol% of the structural unit A formed from the monomer represented by Chemical Formula 1 in the molecule. 1 to 10 mol% of structural units B formed from 4 to 20 mol% (100 mol% in total) of structural units C formed of crosslinkable monomers. The number average molecular weight of the vinyl copolymer M is 7000 to 100,000. When the number average molecular weight is less than 7000, the antistatic property imparted to the thermoplastic polymer molded article becomes insufficient. Conversely, when the number average molecular weight exceeds 100,000, the thermoplastic polymer molded article is uniformly coated. Becomes difficult.

  On the other hand, in the vinyl copolymer N, the structural unit A, the structural unit B, and the structural unit C are the same as those described above for the vinyl copolymer M. The structural unit D is formed from another monomer. Such other monomers are all monomers that can be copolymerized with the monomer represented by Chemical Formula 1 or the polyoxyalkylene-modified monomer or the crosslinkable monomer. 1) unsaturated monobasic acids having 6 to 18 carbon atoms such as octenoic acid, dodecenoic acid, oleic acid, etc. 2) esters of aliphatic alcohols having 1 to 20 carbon atoms and (meth) acrylic acid, 3) maleic acid, Unsaturated dibasic acids having 4 or 5 carbon atoms such as fumaric acid, citraconic acid and mesaconic acid and salts thereof 4) Unsaturated dibasic acids having 4 or 5 carbon atoms such as maleic acid, fumaric acid, citraconic acid and mesaconic acid (Di) esters of acids and aliphatic alcohols having 1 to 20 carbon atoms, 5) unsaturated dibasic acids having 4 or 5 carbon atoms such as maleic acid, fumaric acid, citraconic acid and mesaconic acid, and 2 to 8 carbon atoms (Di) esters with glycols, ) Polyalkylene glycol having an unsaturated dibasic acid having 4 or 5 carbon atoms such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid and a polyoxyalkylene group composed of 2 to 100 oxyalkylene units in the molecule And (di) ester, 7) (meth) acrylamide, N-alkyl (meth) acrylamide substituted with an alkyl group having 1 to 4 carbon atoms, N, N- substituted with an alkyl group having 1 to 4 carbon atoms Unsaturated amides having no crosslinkability such as dialkyl (meth) acrylamide, 8) Vinyl esters such as vinyl acetate and vinyl propionate, 9) Aromatic vinyl monomers such as α-methylstyrene and styrene, 10) Acidic vinyl In molecules such as sulfonic acid, acidic (meth) allyl sulfonic acid, acidic sulfoalkyl (meth) acrylate, acidic styrene sulfonic acid 11) vinyl monomers having acidic sulfonic acid groups, 11) molecules of vinyl sulfonic acid alkali metal salts, (meth) allyl sulfonic acid alkali metal salts, sulfoalkyl (meth) acrylate alkali metal salts, styrene sulfonic acid alkali metal salts, etc. Examples thereof include vinyl monomers having a sulfonic acid alkali metal base. Especially, as other monomers, N-alkyl (meth) acrylamide substituted by C1-C4 aliphatic alcohol and (meth) acrylic acid, the C1-C4 alkyl group, Selected from N, N-dialkyl (meth) acrylamide substituted with an alkyl group having 1 to 4 carbon atoms and (di) esters of unsaturated dibasic acids having 4 or 5 carbon atoms and glycols having 2 to 8 carbon atoms One or more are preferred.

  The vinyl copolymer N is obtained by radical copolymerization of the monomer represented by Chemical Formula 1 described above, a polyoxyalkylene-modified monomer, a crosslinkable monomer, and another monomer. . Such radical copolymerization is the same as described above for the vinyl copolymer M.

  The vinyl copolymer N contains 70 to 94 mol% of the structural unit A formed from the monomer represented by Chemical Formula 1 in the molecule and 1 to 10 of the structural unit B formed from the polyoxyalkylene-modified monomer. It is assumed to have 4 to 20 mol% of the structural unit C formed from a crosslinkable monomer and 1 to 25 mol% (100 mol% in total) of the structural unit D formed from another monomer. . The number average molecular weight of the vinyl copolymer N is 7000 to 100,000. When the number average molecular weight is less than 7000, the antistatic property imparted to the thermoplastic polymer molded article becomes insufficient. Conversely, when the number average molecular weight exceeds 100,000, the thermoplastic polymer molded article is uniformly coated. Becomes difficult.

Next, the antistatic method for the thermoplastic polymer molded body according to the present invention (hereinafter simply referred to as the antistatic method of the present invention) will be described. The antistatic method of the present invention is a method in which the antistatic agent of the present invention described above is adhered in a ratio of 0.01 to 3 g, preferably 0.02 to 1 g, per 1 m ² of the surface of the thermoplastic polymer molded body. It is. Here, per 1 m ² of the surface means per 1 m ^{2 of} one surface or outer surface. When the thermoplastic polymer molding is a flat surface such as a film or a sheet, the surface is per 1 m ² of one surface, and the thermoplastic polymer molding is a three-dimensional shape such as a container or housing. Is per 1 m ² of the outer surface.

In the antistatic method of the present invention, the form of the antistatic agent of the present invention to be used is not particularly limited, but the antistatic agent of the present invention contains water as a main solvent, and if necessary, methyl alcohol, ethyl alcohol, isopropyl alcohol, An aqueous liquid is preferred using a solvent containing a lower alcohol such as butyl alcohol, ethylene glycol or diethylene glycol, a ketone such as acetone or methyl isobutyl ketone, or an ether such as butyl cellosolve, methyl cellosolve or tetrahydrofuran. Also when using this aqueous liquid, it adheres so that it may become a ratio of 0.01-3g as an antistatic agent of this invention per 1 m < ² > of the surface of a thermoplastic polymer molded object, Preferably it is 0.02-1g. Adhesion is mainly related to the shape of the thermoplastic polymer molded body, known as roll coating, gravure coating, air knife coating, bar coating, kiss coating, spray coating, dip coating, etc. Can be applied.

In the antistatic method of the present invention, the antistatic agent of the present invention is applied to a thermoplastic polymer molded body, but as a result, it may be applied to a thermoplastic polymer molded body. For example, it may be applied to an unstretched film or a uniaxially stretched film made of a thermoplastic polymer material that is subjected to a stretching process and then commercialized, or a container made of a thermoplastic polymer material that has been commercialized. It may be applied to a case or a case. Even when applied to an unstretched film or a uniaxially stretched film made of a thermoplastic polymer material that is subsequently subjected to a stretching process to produce a product, the application amount of the antistatic agent of the present invention becomes a product after the stretching process. The ratio is 0.01 to 3 g, preferably 0.02 to 1.0 g, per 1 m ^{2 of the} thermoplastic polymer film, that is, the thermoplastic polymer molded body. In application, a binder resin, a surfactant, an antioxidant, an ultraviolet absorber, a lubricant, a crosslinking agent, and the like can be used in combination as long as the effects of the present invention are not impaired.

  The antistatic method of the present invention can be applied to various shapes of thermoplastic polymer moldings produced using various thermoplastic polymer materials. Such thermoplastic polymer materials include: 1) polyester polymer materials such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene naphthalate, 2) polycarbonate polymer materials, 3) polystyrene, acrylonitrile-styrene copolymer Polystyrene polymer materials such as polymers, acrylonitrile-butadiene-styrene copolymers (hereinafter simply referred to as ABS), 4) polyacrylic polymer materials such as polymethyl methacrylate (hereinafter simply referred to as PMMA), 5) polyvinyl chloride, Polyvinyl polymer materials such as polyvinyl acetate, 6) Polyolefin polymer materials such as polyethylene and polypropylene (hereinafter simply referred to as PP), 7) Nylon 6, Nylon 11, Nylon 12, Nylon 6, 6, Nylon 6 10, polyamide of 1,3-bis (aminomethyl) cyclohexane and aliphatic dicarboxylic acid, polyamide of aliphatic diamine and 1,4-cyclohexanedicarboxylic acid, poly-p-phenylene terephthalamide, poly-m-phenylene iso Examples thereof include polyamide polymer materials such as phthalamide, 8) polymer blends of two or more thermoplastic polymer materials selected from the above 1) to 7), and thermoplastic polymer materials such as polymer alloys. Among these, the antistatic agent of the present invention is one or more selected from polycarbonate polymer materials, polystyrene polymer materials, polyacrylic polymer materials, polyvinyl polymer materials, and polyolefin polymer materials. The effect is high when applied to a thermoplastic polymer molded body produced from the above thermoplastic polymer material. When applying the antistatic agent of the present invention, the thermoplastic polymer material as described above includes inorganic fillers such as titanium oxide, talc, aluminum oxide, calcium carbonate, and silicone, a crosslinked polystyrene resin, a crosslinked acrylic resin, a urea resin, Even if it contains organic fillers such as melamine resin and silicone resin, antioxidants, ultraviolet absorbers, fluorescent brighteners, lubricants, flame retardants, etc., there is no problem.

Finally, the antistatic thermoplastic polymer molded product according to the present invention (hereinafter simply referred to as the antistatic molded product of the present invention) will be described. The antistatic molded article of the present invention is formed by adhering the above-described antistatic agent of the present invention at a ratio of 0.01 to 3 g, preferably 0.02 to 1 g, per 1 m ² of the surface of the thermoplastic polymer molded article. Is. In the antistatic molded article of the present invention, a thermoplastic polymer molded article, the meaning per 1 m ^{2 of} the surface thereof, a thermoplastic polymer material used for producing the thermoplastic polymer molded article, and particularly preferred thermoplastic polymers. The materials and the like are the same as described above for the antistatic method of the present invention.

  According to the antistatic agent of the present invention, the thermoplastic polymer molded article can be imparted with a sufficiently durable antistatic property even under low humidity, and at the same time, the thermoplastic polymer molded article can be reused, and has high thermoplasticity. There is an effect that the coating property to the molecular molded body, the non-transferability from the thermoplastic polymer molded body, the blocking resistance between the thermoplastic polymer molded bodies, and the non-tack property of the thermoplastic polymer molded body are excellent.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test Category 1 (Synthesis of vinyl copolymer as antistatic agent)
Example 1 {Synthesis of vinyl copolymer (M-1)}
The reaction vessel was charged with 340 g of water, and the inside of the reaction vessel was purged with nitrogen to 80 ° C., and then 226.6 g (0.95 mol) of acryloyloxyethyldimethylammonium methylsulfonate, methoxypolyethylene glycol (oxy) Ethylene unit repeat number 23) Vinyl monomer aqueous solution consisting of 62.1 g (0.056 mol) methacrylate, 11.3 g (0.11 mol) N-methylolacrylamide and 300 g water, and 30 g 5% ammonium persulfate aqueous solution Were simultaneously added dropwise over 2 hours to carry out radical copolymerization reaction. Next, 30 g of 5% ammonium persulfate aqueous solution was added over 1 hour, and then the radical copolymerization reaction was continued for 6 hours while maintaining the reaction temperature at 80 ° C. to obtain a reaction product. As a result of purifying and analyzing a part of the reaction product, R ^{1 in} Chemical Formula ¹ is a hydrogen atom, R ² is a methyl group, R ³ is a methyl group, R ⁴ is a methyl group, A is a carbonyloxy group, and B is ethylene. group, X ^- is methyl sulfonic acid 85 mol% of structural units formed from the monomer represented by the formula 1 when an ionic group (E-1), R ⁵ is a methyl group in Chemical Formula 2, R ⁶ A monomer represented by the chemical formula 2 in which is a methyl group and D ¹ is a residue obtained by removing all hydroxyl groups from a polyoxyethylene diol having a polyoxyethylene group composed of 23 oxyethylene units in the molecule. From the monomer (I-1) represented by chemical formula 5 when the structural unit formed from the compound (F-1) is 5 mol%, R ¹¹ in chemical formula 5 is a hydrogen atom, and R ¹² is a hydrogen atom Number-average molecule having 10 mol% (100 mol% in total) of the formed structural units The amount of vinyl copolymer (M-1) was 30000. This was designated as an antistatic agent (M-1).

Examples or Reference Examples 2 to 23 and Comparative Examples 1 to 6 {vinyl copolymers (M-2) to (M-11), (N-1) to (N-12) and (R-1) to Synthesis of (R-6)}
In the same manner as the vinyl copolymer (M-1) of Example 1, the vinyl copolymers (M-2) to (M-11) of Examples or Reference Examples 2 to 11, and the Examples or Reference Examples 12 to 23 vinyl copolymers (N-1) to (N-12) and vinyl copolymers (R-1) to (R-6) of Comparative Examples 1 to 6 were synthesized. These were designated as antistatic agents (M-2) to (M-11), (N-1) to (N-12) and (R-1) to (R-6), respectively. These contents including the vinyl copolymer (M-1) are summarized in Table 1.

In Table 1,
* 1: Type of vinyl copolymer (antistatic agent) * 2: Type of monomer that forms the structural unit A * 3: Polyoxyalkylene-modified monomer that forms the structural unit B * 4: Type of the crosslinkable monomer that will form the structural unit C * 5: Type of other monomer that will form the structural unit D Ratio: Unit is mol%
Monomers (E-1) to (E-10): Monomers represented by Chemical Formula 1 whose contents are summarized in Table 2 below. Monomers (F-1) to (F-4): Monomers represented by Chemical Formula 2 whose contents are summarized in Table 3 of the following: Monomers (G-1) to (G-4): Shown by Chemical Formula 3 below whose contents are summarized in Table 4 below. Monomers (H-1) to (H-4): Monomers represented by the following chemical formula 4 whose contents are summarized in Table 5 below: Monomers (I-1) to ( I-4): Monomers represented by Chemical Formula 5 whose contents are collectively shown in Table 6 below. Monomers (J-1) to (J-4): The contents are collectively shown in Table 7 below. Monomer represented by Chemical Formula 6 Monomers (K-1) to (K-4): Monomers represented by Chemical Formula 7 whose contents are summarized in Table 8 below Monomer (L-1) To (L-4): indicated by the chemical formula 8 whose contents are summarized in Table 9 below. Q-1: Ethyl acrylate Q-2: N-ethylacrylamide Q-3: N, N-dimethylacrylamide Q-4: Diethyl maleate Q-5: Acrylamide Q-6: Vinyl acetate Q-7 : Sodium styrenesulfonate

In Table 2,
A-1: Carbonyloxy group A-2: Carbonylamino group B-1: Ethylene group B-2: Trimethylene group B-3: Tetramethylene group B-4: Hexamethylene group X-1: Methylsulfonic acid ion group X -2: Ethylsulfonic acid ion group X-3: Nitrate ion group Z-1: 2-hydroxyethyl group Z-2: 3-hydroxypropyl group

In Tables 3-5,
D-1: All hydroxyl groups were removed from polyoxyethylene diol having a polyoxyethylene group composed of 23 oxyethylene units in the molecule (m = 23, m is the number of oxyethylene units, the same applies hereinafter). Residue D-2: Residue obtained by removing all hydroxyl groups from polyoxyethylene diol (m = 9) D-3: Polyoxypropylene having a polyoxypropylene group composed of 6 oxypropylene units in the molecule Residue obtained by removing all hydroxyl groups from a diol (n = 6, n is the number of oxypropylene units, the same applies hereinafter) D-4: Polyoxyalkylene diol (random type, m = 20, n = 20, m + n = 40) Residues from which all hydroxyl groups are removed

In Tables 7-9,
Y-1: residue obtained by removing one hydroxyl group from diethylene glycol Y-2: residue obtained by removing one hydroxyl group from triethylene glycol Y-3: residue obtained by removing one hydroxyl group from tripropylene glycol

Test Category 2 (Application of antistatic agent to polyethylene terephthalate film and its evaluation)
-Application of antistatic agent to polyethylene terephthalate film Polyethylene terephthalate having an intrinsic viscosity of 0.65 was melt extruded at 280 to 300 ° C and cooled with a cooling roll at 15 ° C to obtain an unstretched film. This unstretched film was uniaxially stretched 3.5 times in the longitudinal direction between a pair of 85 ° C. rolls having different peripheral speeds to obtain a uniaxially stretched film. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid was applied to a uniaxially stretched film by a kiss coating method so that the coating amount shown in Table 10 per 1 m ² of the surface of the biaxially stretched film that was further stretched was 70 ° C. To obtain a uniaxially stretched coated polyester film. Finally, the uniaxially stretched coated polyester film was stretched 3.5 times in the transverse direction at 98 ° C. with a tenter and heat-set at 200 to 210 ° C. to obtain a biaxially stretched coated polyester film having a thickness of 100 μm as a product. . The following evaluation was performed about the obtained uniaxially stretched or biaxially stretched coated polyester film. The results are summarized in Table 10.

・ Evaluation of antistatic property Condition 1
The uniaxially stretched coated polyester film was conditioned at 20 ° C. under conditions of 50% relative humidity for 24 hours, and then surface resistivity (Ω) was measured under the same conditions using a surface resistance value measuring device (trade name, manufactured by Sicid Electric Co., Ltd.). It was measured using Megaresta HT-301) and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ⁹ Ω ○: Surface specific resistance is 1 × 10 ⁹ Ω or more and less than 1 × 10 ¹⁰ Ω Δ: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω ×: Surface resistivity is 1 × 10 ¹¹ Ω or more

Condition 2
The biaxially stretched coated polyester film was evaluated in the same manner as in Condition 1.

Condition 3
The biaxially stretched coated polyester film is conditioned at 20 ° C. under a relative humidity of 30% for 24 hours, and the surface specific resistance (Ω) is measured under the same conditions by using a surface resistance value measuring device (commercially available from Cishido Electric Co., Ltd.). No. Megaresta HT-301) was measured and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ¹⁰ Ω ○: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω Δ: Surface specific resistance is 1 × 10 ¹¹ Ω or more and less than 1 × 10 ¹² Ω ×: Surface specific resistance is 1 × 10 ¹² Ω or more

Evaluation of reusability The above-mentioned biaxially stretched coated polyester film was pulverized and melted at about 300 ° C. with an extruder to form chips. A melt film was formed using this chip to produce a recycled film. Separately, a recycled film was produced using a biaxially stretched coated polyester film coated with only water as a blank. The reusability was evaluated according to the following criteria from the degree of coloring of both recycled films.
Evaluation criteria ◎: Equivalent to blank and almost uncolored ○: Slightly colored compared to blank, but no problem in reuse △: Clearly colored compared to blank , There are restrictions on reuse ×: Remarkably colored compared to blank, and cannot be reused

-Evaluation of applicability The surface of the biaxially stretched coated polyester film was observed with the naked eye and evaluated according to the following criteria.
Evaluation Criteria A: Uniform coating film without omission of coating O: Almost no coating omission but almost uniform coating film Δ: There is some coating omission, but almost uniform coating as a whole It is a film. X: There are many coating omissions and it is an uneven coating film

Evaluation of non-transferability A sample piece cut into a 20 cm × 20 cm square from the uniaxially stretched coated polyester film and a non-coated uniaxially stretched polyester film were stacked on the coating surface, and a load of 1 kg / m ² was applied evenly. After conditioning for 60 hours at 20 ° C. under a relative humidity of 50%, the surface resistivity (Ω) of the coating surface of the sample piece was measured under the same conditions by using a surface resistance measuring device (trade name Megaresta HT- manufactured by Sicid Electric Co., Ltd.). 301) and evaluated according to the following criteria.
Evaluation criteria A: Surface specific resistance is less than 1 × 10 ⁹ Ω ○: Surface specific resistance is 1 × 10 ⁹ Ω or more and less than 1 × 10 ¹⁰ Ω Δ: Surface specific resistance is 1 × 10 ¹⁰ Ω or more and less than 1 × 10 ¹¹ Ω ×: Surface resistivity is 1 × 10 ¹¹ Ω or more

· A uniaxially stretched polyester film of a uniaxial oriented coating polyester film blocking resistance evaluation the not specimen and the coating process was cut into a square of 20 cm × 20 cm overlap with the coating surface, toward uniform load 1 kg / m ^2, After holding at 50 ° C. for 24 hours, the film was cut to a width of 10 mm, the peel strength between the sample piece and the uncoated film was measured, and the blocking resistance was evaluated according to the following criteria.
Evaluation criteria A: Peeling force less than 5 gf / 10 mm O: Peeling force 5 gf / 10 mm or more, less than 8 gf / 10 mm Δ: Peeling force 8 gf / 10 mm or more, less than 15 gf / 10 mm ×: Peeling force 15 gf / 10 mm or more

In Table 10,
Ratio:% by mass in antistatic agent (hereinafter the same)
Application amount: Adhesion amount (g) as an antistatic agent per 1 m ^{2 of a} biaxially stretched film as a product (hereinafter the same)
R-7: a polycationic polymer having a number average molecular weight of 32,000 having s pyrrolidinium ring represented by the following chemical formula 9 in the molecule (hereinafter the same)
R-8: a polycation polymer having a number average molecular weight of 23,000 having t pyrrolidinium rings represented by the following chemical formula 10 in the molecule (hereinafter the same)

Test category 3 (Application of antistatic agent to polycarbonate sheet and its evaluation)
-Application of antistatic agent to polycarbonate sheet Polycarbonate is put into a twin-screw extruder, melted and kneaded at 280 ° C, and cast onto a 30 ° C cooling roll by the T-die method to produce a polycarbonate sheet with a thickness of 1 mm. did. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid was applied by a kiss coating method so as to have the coating amount shown in Table 11 per 1 m ² of the surface of the polycarbonate sheet, and dried with hot air at 150 ° C. for 1 minute to be antistatic treated. A polycarbonate sheet was obtained. The following evaluation was performed on this antistatic treated polycarbonate sheet. The results are summarized in Table 11.

・ Evaluation of antistatic property Condition 1
The antistatic property of the polycarbonate sheet subjected to the antistatic treatment was evaluated in the same manner as in Condition 1 of Test Category 2.

Condition 2
The antistatic polycarbonate sheet was conditioned at 20 ° C. under a relative humidity of 40% for 24 hours, and the surface specific resistance (Ω) was measured under the same conditions by using a surface resistance measuring device (manufactured by Cishido Electric Co., Ltd.). It measured using the brand name Megaresta HT-301) and evaluated on the following reference | standard.
Evaluation criteria A: Surface specific resistance is less than 2 × 10 ⁹ Ω ○: Surface specific resistance is 2 × 10 ⁹ Ω or more and less than 2 × 10 ¹⁰ Ω Δ: Surface specific resistance is 2 × 10 ¹⁰ Ω or more and less than 2 × 10 ¹¹ Ω ×: Surface specific resistance is 2 × 10 ¹¹ Ω or more

Condition 3
The antistatic property of the polycarbonate sheet subjected to the antistatic treatment was evaluated in the same manner as in Condition 3 of Test Category 2.

Evaluation of reusability The above-mentioned antistatic-treated polycarbonate sheet was pulverized and melted at about 280 ° C. with an extruder to form chips. This chip was used to melt and form a recycled sheet. Separately, a recycled sheet was produced using a polycarbonate sheet coated with only water as a blank. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled sheets.

-Evaluation of applicability The applicability of the antistatic polycarbonate sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of non-transferability About the polycarbonate sheet by which the said antistatic process was carried out, the non-transferability was evaluated similarly to the test category 2.

-Evaluation of blocking resistance About the said polycarbonate sheet by which antistatic treatment was carried out, the blocking resistance was evaluated similarly to the test division 2. FIG.

Test Category 4 (Application of antistatic agent to ABS sheet and its evaluation)
-Application of antistatic agent to ABS sheet ABS is put into a twin screw extruder, melt-kneaded at 220 ° C, and cast on a 30 ° C cooling roll by the T-die method to produce an ABS sheet with a thickness of 1mm. did. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of an aqueous solution is applied by the kiss coating method so as to have the coating amount shown in Table 12 per 1 m ² of the surface of the ABS sheet, and dried with hot air at 150 ° C. for 1 minute to be antistatic treated. An ABS sheet was obtained. The following evaluation was performed on the antistatic treated ABS sheet. The results are summarized in Table 12.

Evaluation of antistatic property The antistatic property of the ABS sheet subjected to the antistatic treatment was evaluated in the same manner as in Test Category 3.

Evaluation of reusability The antistatic ABS sheet was crushed and melted at about 220 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled ABS sheet. Separately, a recycled ABS sheet was produced using an ABS resin sheet coated only with water as a blank. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled ABS sheets.

-Evaluation of applicability The applicability of the antistatic ABS sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of non-transferability The non-transferability of the antistatic ABS sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of blocking resistance The antistatic ABS sheet was evaluated for blocking resistance in the same manner as in Test Category 2.

Test Category 5 (Application of antistatic agent to PMMA sheet and its evaluation)
-Application of antistatic agent to PMMA sheet PMMA is put into a twin screw extruder, melted and kneaded at 230 ° C, and cast on a 30 ° C cooling roll by the T-die method to produce a PMMA sheet with a thickness of 1 mm. did. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid was applied by the kiss coating method so as to have the coating amount shown in Table 13 per 1 m ² of the surface of the PMMA sheet, dried with hot air at 150 ° C. for 1 minute, and subjected to antistatic treatment. A PMMA sheet was obtained. The following evaluation was performed on this antistatic PMMA sheet. The results are summarized in Table 13.

Evaluation of antistatic property The antistatic property of the PMMA sheet subjected to the antistatic treatment was evaluated in the same manner as in Test Category 3.

Evaluation of reusability The antistatic PMMA sheet was crushed and melted at about 230 ° C. with an extruder to form a chip. Using this chip, melt film formation was performed to produce a recycled PMMA sheet. Separately, a regenerated PMMA sheet was produced using a PMMA sheet coated only with water as a blank. Reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled PMMA sheets.

-Evaluation of applicability The applicability of the antistatic PMMA sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of non-transferability About the said PMMA sheet by which the antistatic process was carried out, the non-transferability was evaluated similarly to the test category 2.

-Evaluation of blocking resistance The anti-blocking PMMA sheet was evaluated for blocking resistance in the same manner as in Test Category 2.

Test Category 6 (Application of antistatic agent to polyvinyl chloride sheet and its evaluation)
Application of antistatic agent to polyvinyl chloride sheet After adding 40 parts of di-2-ethylhexyl phthalate as a plasticizer to a mixer per 100 parts of polyvinyl chloride, 2 parts of barium stearate and stearic acid as stabilizers 1 part of zinc was added and mixed. The mixture was melt-kneaded by a twin screw extruder to produce a polyvinyl chloride sheet having a thickness of 2 mm by the T-die method. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid was applied by the kiss coating method so as to have the coating amount shown in Table 14 per 1 m ^{2 of the} polyvinyl chloride sheet, and dried with hot air at 100 ° C. for 1 minute to be antistatic treated. A polyvinyl chloride sheet was obtained. The following evaluation was performed on this antistatic treated polyvinyl chloride sheet. The results are summarized in Table 14.

-Evaluation of antistatic property About the polyvinyl chloride sheet by which the said antistatic treatment was carried out, the antistatic property was evaluated similarly to the test category 3.

Evaluation of reusability The antistatic treated polyvinyl chloride sheet was pulverized and melted at about 180 ° C. with an extruder to form chips. Using this chip, a melt film was formed to produce a recycled polyvinyl chloride sheet. Separately, a recycled polyvinyl chloride sheet was produced using a polyvinyl chloride sheet coated only with water as a blank. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled polyvinyl chloride sheets.

-Evaluation of applicability The applicability of the antistatic polyvinyl chloride sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of non-transferability About the said polyvinyl chloride sheet by which antistatic treatment was carried out, the non-transferability was evaluated similarly to the test category 2.

-Evaluation of blocking resistance The anti-blocking polyvinyl chloride sheet was evaluated for blocking resistance in the same manner as in Test Category 2.

Test category 7 (Application of antistatic agent to PP sheet and its evaluation)
・ Applying antistatic agent to PP sheet Polypropylene is put into a twin screw extruder, melt kneaded at 250 ° C, and cast onto a 30 ° C cooling roll by the T-die method to produce a PP sheet with a thickness of 1 mm. did. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid was applied by the kiss coating method so as to have the coating amount shown in Table 15 per 1 m ² of the surface of the PP sheet, and dried with hot air at 100 ° C. for 1 minute to be antistatic treated. A PP sheet was obtained. The following evaluation was performed on this antistatic treated PP sheet. The results are summarized in Table 15.

Evaluation of antistatic property The antistatic property was evaluated in the same manner as in Test Category 3 for the antistatic treated PP sheet.

Evaluation of reusability The antistatic treated PP sheet was pulverized and melted at about 230 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled PP sheet. Separately, a recycled PP sheet was produced using a PP sheet coated only with water as a blank. From the degree of coloring of both recycled PP sheets, reusability was evaluated in the same manner as in Test Category 2.

-Evaluation of applicability The applicability of the antistatic PP sheet was evaluated in the same manner as in Test Category 2.

Evaluation of non-transferability The non-transferability of the antistatic PP sheet was evaluated in the same manner as in Test Category 2.

-Evaluation of blocking resistance The antistatic PP sheet was evaluated for blocking resistance in the same manner as in Test Category 2.

Test Category 8 (Application of antistatic agent to polyethylene terephthalate molding and its evaluation)
-Application of antistatic agent to polyethylene terephthalate molded body Polyethylene terephthalate was injection molded at 290 to 300 ° C to prepare a polyethylene terephthalate molded body having a length of 15 cm x width of 2 cm and a thickness of 4 mm. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a 5% aqueous liquid was applied by a spray method so that the coating amount shown in Table 16 per 1 m ² of the surface of the polyethylene terephthalate molded body was dried with hot air at 150 ° C. for 1 minute, and antistatic treatment A polyethylene terephthalate molded body was obtained. The following evaluation was performed on this antistatic-treated polyethylene terephthalate molded body. The results are summarized in Table 16.

-Evaluation of antistatic property About the polyethylene terephthalate molded object by which the said antistatic process was carried out, the antistatic property was evaluated similarly to the test category 3.

Evaluation of reusability The antistatic-treated polyethylene terephthalate molded body was pulverized and melted at about 300 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled polyethylene terephthalate sheet. Separately, a recycled polyethylene terephthalate sheet was produced using a polyethylene terephthalate molded body coated only with water as a blank. From the degree of coloring of both recycled polyethylene terephthalate sheets, reusability was evaluated in the same manner as in Test Category 2.

-Evaluation of applicability The surface of the antistatic-treated polyethylene terephthalate molded body was observed with the naked eye and evaluated according to the following criteria.
Evaluation criteria ◎: There is no cissing and it is a uniform coating film ○: There is very little cissing, but it is almost uniform coating film △: There is some cissing, but the coating film is almost uniform as a whole ×: There are many repellent and non-uniform coating films

Evaluation of non-transferability The antistatic-treated polyethylene terephthalate molded body and the untreated polyethylene terephthalate molded body not subjected to antistatic treatment are stacked on the surface to which the antistatic agent is applied, and a load of 1 kg / m ² is applied evenly. The surface resistivity of the surface coated with the antistatic agent of the polyethylene terephthalate molded body that was antistatic treated under the same conditions for 60 hours at 20 ° C and 50% relative humidity was measured. Measurement was performed using an apparatus (trade name Megaresta HT-301 manufactured by Sicid Electric Co., Ltd.), and non-transferability was evaluated in the same manner as in Test Category 2.

-Evaluation of non-tack property The non-tack property of the antistatic-treated polyethylene terephthalate molding was evaluated according to the following criteria.
Evaluation criteria ◎: No stickiness and good surface ○: Slightly sticky, usable level △: Some stickiness, limited use ×: Clear stickiness, I can not use it

Test category 9 (Application of antistatic agent to polycarbonate molding and its evaluation)
-Application | coating of the antistatic agent to a polycarbonate molded object Polycarbonate was injection-molded at 290-300 degreeC, and the polycarbonate molded object of length 15cm x width 2cm x thickness 4mm was produced. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid is applied by a spray method so as to have the coating amount shown in Table 17 per 1 m ² of the surface of a polycarbonate molded body, dried with hot air at 150 ° C. for 1 minute, and antistatic treated. A polycarbonate molded body was obtained. The following evaluation was performed on the polycarbonate molded body subjected to the antistatic treatment. The results are summarized in Table 17.

-Evaluation of antistatic property The antistatic property was evaluated in the same manner as in Test Category 3 for the above-mentioned polycarbonate molded body subjected to the antistatic treatment.

Evaluation of reusability The above-mentioned antistatic-treated polycarbonate molded body was pulverized and melted at about 280 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled polycarbonate sheet. Separately, a recycled polycarbonate sheet was produced using a polycarbonate molded body coated only with water as a blank. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled polycarbonate sheets.

-Evaluation of applicability The applicability was evaluated in the same manner as in Test Category 8 for the above-mentioned polycarbonate molded body subjected to the antistatic treatment.

-Evaluation of non-transferability The non-transferability was evaluated in the same manner as in Test Category 8 for the above-mentioned polycarbonate molded body subjected to the antistatic treatment.

-Evaluation of non-tack property The non-tack property was evaluated similarly to the test division 8 about the polycarbonate molded object by which the said antistatic process was carried out.

Test category 10 (Application of antistatic agent to ABS molded body and its evaluation)
Application of antistatic agent to ABS molded body ABS was injection molded at about 220 ° C. to prepare an ABS molded body of 15 cm long × 2 cm wide × 4 mm thick. Next, 5 parts of polyoxyethylene (m = 10) monononylphenyl ether prepared separately in 100 parts of 5% aqueous liquid obtained by diluting the vinyl copolymer or the like (antistatic agent) synthesized in Test Category 1 with water. A mixture of 5 parts of a% aqueous liquid is applied by a spray method so as to have the coating amount shown in Table 18 per 1 m ² of the surface of the ABS molded body, dried with hot air at 100 ° C. for 1 minute, and antistatic treated. An ABS molded body was obtained. The antistatic-treated ABS molded body was evaluated as follows. The results are summarized in Table 18.

Evaluation of antistatic property The antistatic property of the ABS molded body subjected to the antistatic treatment was evaluated in the same manner as in Test Category 3.

Evaluation of reusability The antistatic-treated ABS molded body was pulverized and melted at about 230 ° C. with an extruder to form a chip. This chip was used to melt and form a recycled ABS sheet. Separately, as a blank, a recycled ABS sheet was produced using an ABS molded body to which only water was applied. The reusability was evaluated in the same manner as in Test Category 2 from the degree of coloring of both recycled ABS sheets.

-Evaluation of applicability The applicability of the antistatic ABS molded body was evaluated in the same manner as in Test Category 8.

-Evaluation of non-transferability About the said ABS molded object by which the antistatic process was carried out, the non-transferability was evaluated similarly to the test classification 8.

-Evaluation of non-tack property About the ABS molded object by which the said antistatic process was carried out, the non-tack property was evaluated similarly to the test classification 8.

Claims (11)

An antistatic agent for a thermoplastic polymer, comprising one or more selected from the following vinyl copolymer M and the following vinyl copolymer N.
Vinyl copolymer M: 70 to 95 mol% of a structural unit A formed from the monomer represented by the following chemical formula 1 in the molecule, and a structural unit B formed from the following polyoxyalkylene-modified monomer A vinyl copolymer having a number average molecular weight of 7000 to 100,000 having a structural unit C of 4 to 20 mol% (total of 100 mol%) formed from 1 to 10 mol% and the following crosslinkable monomer Vinyl copolymer N: 70 to 94 mol% of the structural unit A formed from the monomer represented by the following chemical formula 1 in the molecule, 1 to 10 mol% of the structural unit B formed from the following polyoxyalkylene-modified monomer, 4 to 20 mol% of a structural unit C formed from the following crosslinkable monomer and a monomer represented by the following chemical formula 1 or the following polyoxyalkylene-modified monomer or the following crosslinkable monomer: Formed from copolymerizable monomers Vinyl copolymer polyoxyalkylene-modified monomer of structural unit D of 1 to 25 mol% (total of 100 mol%) Number-average molecular weight having from 7,000 to 100,000: polyoxyalkylene-modified monomer represented by the following chemical formula 2 one or more crosslinking monomer selected pressurized et: crosslinkable monomer represented by Formula 5 below, the crosslinkable monomer represented by Chemical Formula 6 below, represented by Chemical Formula 7 below bridge One or two or more selected from a crosslinkable monomer represented by the following chemical formula 8

{In Chemical Formulas 1 through 8,
R ¹ , R ⁵ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ : hydrogen atom or methyl group R ² , R ³ , R ⁴ : hydroxyalkyl having 2 or 3 carbon atoms in hydrogen atom, methyl group or alkyl group Group (however, at least two of R ^{2 to} R ⁴ are a methyl group or a hydroxyalkyl group having 2 or 3 carbon atoms in an alkyl group)
R ^6: a carbon number of 1 to 12 alkyl group R ¹² of: alkyl groups R ¹³ a hydrogen atom or 1 to 6 carbon: hydrogen atom, a methyl group or a carboxyl group A: carbonyl group or carbonylamino group B: 2 carbon atoms ~ 6 alkylene groups
D ^1: residue obtained by removing all hydroxyl groups from poly ethylene glycol having a polyoxy ethylene alkylene group composed of a total of 9-35 oxyethylene units of the molecule X ^-: nitrate ion group or an alkyl group alkylsulfonate ion group Y 1 having 1 to 4 carbon ^atoms: hydrogen atom, a hydroxyalkyl group having 1 to 6 carbon atoms, a total of 1 to 3 in the organic radical or molecule having 3 to 10 carbon atoms having an epoxy group Residue obtained by removing one hydroxyl group from a (poly) oxyalkylene diol having a (poly) oxyalkylene group composed of oxyethylene units and / or oxypropylene units Y ² : an organic group having 3 to 10 carbon atoms having an epoxy group A group or molecule having a (poly) oxyalkylene group composed of a total of 1 to 3 oxyethylene units and / or oxypropylene units (poly Oxyalkylene residues Y except for one hydroxyl group from all ^3: a hydrogen atom, a total of 1-3 oxyethylene units in the organic radical or molecule having 3 to 10 carbon atoms having an epoxy group and / or oxypropylene units Residue obtained by removing one hydroxyl group from a (poly) oxyalkylenediol having a constructed (poly) oxyalkylene group} Of the monomer represented by 1, of 1 in wherein X ^- thermoplastic polymer antistatic agent according to claim 1, wherein one where a nitrate group or a methyl sulfonate ion group.   The antistatic agent for thermoplastic polymers according to claim 1 or 2, wherein the monomer represented by Chemical Formula 1 is a monomer in which B in Chemical Formula 1 is an ethylene group or a trimethylene group. The antistatic agent for thermoplastic polymers according to any one of claims 1 to 3 , wherein the crosslinkable monomer is a crosslinkable monomer represented by Chemical formula 5. A monomer copolymerizable with a monomer represented by Chemical Formula 1, a polyoxyalkylene-modified monomer or a crosslinkable monomer is an ester of an aliphatic alcohol having 1 to 4 carbon atoms and (meth) acrylic acid N-alkyl (meth) acrylamide substituted with an alkyl group having 1 to 4 carbon atoms, N, N-dialkyl (meth) acrylamide substituted with an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 4 or 5 carbon atoms. The antistatic agent for thermoplastic polymers according to any one of claims 1 to 4 , which is one or more selected from (di) esters of a saturated dibasic acid and a glycol having 2 to 8 carbon atoms. . The antistatic agent for thermoplastic polymers according to any one of claims 1 to 5 is attached so as to have a ratio of 0.01 to 3 g per 1 m ² of the surface of the thermoplastic polymer molded body. An antistatic method for forming a thermoplastic polymer molded body. The antistatic agent for thermoplastic polymers is made into an aqueous liquid, and the aqueous liquid is charged for the thermoplastic polymer per 1 m ² of the surface of a thermoplastic polymer molded body produced using the following thermoplastic polymer material. The method for preventing static charge of a thermoplastic polymer molded article according to claim 6 , wherein the thermoplastic polymer molded article is adhered so as to have a ratio of 0.01 to 3 g as an inhibitor.
Thermoplastic polymer material: one or two selected from polyester polymer material, polycarbonate polymer material, polystyrene polymer material, polyacrylic polymer material, polyvinyl polymer material and polyolefin polymer material more than The method for preventing static charge of a thermoplastic polymer molded article according to claim 6 or 7 , wherein the thermoplastic polymer molded article is a thermoplastic polymer film or sheet. The antistatic agent for thermoplastic polymers according to any one of claims 1 to 5 is adhered at a rate of 0.01 to 3 g per 1 m ² of the surface of the thermoplastic polymer molded body. Antistatic thermoplastic polymer molded body. The antistatic thermoplastic polymer molded article according to claim 9 , wherein the thermoplastic polymer molded article is produced using the following thermoplastic polymer material.
Thermoplastic polymer material: one or two selected from polyester polymer material, polycarbonate polymer material, polystyrene polymer material, polyacrylic polymer material, polyvinyl polymer material and polyolefin polymer material more than The antistatic thermoplastic polymer molding according to claim 9 or 10 , wherein the thermoplastic polymer molding is a thermoplastic polymer film or sheet.